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Lecture 2: Point Groups

Point groups are a shorthand means of summarising all of the symmetry properties of a given
molecule (or any other object). Thus, molecules that are, at first glance, very different from each
other may turn out to be closely related in terms of their symmetry. Consider the molecules below:

Despite their obvious differences, these molecules all have the same set of symmetry elements; a
two-fold axis (C2) and two vertical mirror planes (v), as shown in the diagram below for H2O:

These three symmetry elements together with the identity operation


(E), give rise to four symmetry operations: E, C2, v and v’. Remember
that C22 = E and note that the two reflections have different effects on
the molecule; one (v) leaves the atoms unchanged as it is in the plane
of the molecule, whereas the other (v’) results in the two hydrogen
atoms swapping places. Thus these reflections can not be grouped
together into a class and one is given a prime (‘) to differentiate it from
the other. We can also differentiate these operations by applying a
coordinate system as we shall see later.

Since many properties of a molecule (e.g. the arrangement of its


molecular orbitals, the pattern of its stretching vibrations or its dipole
moment) are related to its overall symmetry, it follows that molecules with the same symmetry will
have certain fundamental similarities in some of their other properties. It is thus convenient to
classify molecules according to their symmetry properties and this is why point groups are so useful.
Since the five molecules shown above all have the same set of symmetry properties, they belong to
the same point group which, in this case, is denoted C2v.

Point group notation is a shorthand method for expressing the key symmetry properties of a
molecule. Remember from Lecture 1 that the presence of certain symmetry elements may be a
consequence of the presence of others. Thus for C2v, the presence of a C2 axis and one vertical
symmetry plane means that any C2v molecule must also have another vertical plane, v’, since
C2.v = v’. The name of the group, C2v, is therefore used to describe a set of symmetry properties
(E, C2, v and v’, not all of which are independent of each other) and contains a considerable
amount of information; from the group’s name you should be able to guess that the group contains
a C2 axis and at least one vertical mirror plane, from which the presence of the other mirror plane
necessarily follows.
For the Mathematically Curious
These notes are provided for people who are curious about the mathematical properties of groups. It is not
material that will be examined in its own right.
Point groups obey all the mathematical rules pertaining to a group and its operations. Four important
properties that all groups possess are:
Closure
Any sequence of two operations is equivalent to performing another operation of the group. Thus a table
can be drawn up that shows the effect of performing one operation followed by another:
C2v E C2 v v’
E E C2 v v’
C2 C2 E v’ v
v v v’ E C2
v’ v’ v C2 E
Identity
One operation in the group must have the effect of doing nothing. Thus all point groups contain the identity
operator E
Inverses
After performing an operation, there must be an operation that can reverse the operation performed. In
other words there must for any operator A be an operator B that can subsequently be performed to give the
identity operation E. Some point groups (including C2v) have self-inverses (e.g. performing the C2 operation
twice results in E).
Associativity
For three operations A, B and C, the following must be true:
A.(B.C) = (A.B).C
For example, in the point group C2v:
(C2.v).v’
= v’.v’
=E
is the same as:
C2.(v.v’)
= C2.C2
=E

We could identify the point group of a molecule by laboriously identifying all of the symmetry
operations that the molecule contains – as you did in Workshop 1. However, it is much quicker to
identify only the key symmetry operations from which the others follow. A method for finding the
point group that you must learn is given below.

The method is given as a set of instructions and as a flow chart. Some of you may find it easier to
memorise the instructions, others may find the flow chart more useful. Either way you must learn
and memorise how to determine the point group so that you can determine the point group from
memory without referring to these instructions. This is best done by practising using the example
molecules given in this handout and in Workshop 2.
Determining the Point Group
1) First of all, consider special cases. These are usually very obvious.
a) Does the molecule have more than one highest-order rotation axis Cn with n > 2?
If n= 3, then the molecule has Tetrahedral symmetry (T):

If there are mirror planes that include two C3 axes, then the point group is Td
If there is a centre of symmetry (i), then the point group is Th
Otherwise, the point group is just T.
If n = 4, then the molecule has Octahedral symmetry (O):
If there are mirror planes perpendicular to the C4 axes, then the point group is Oh
Otherwise, the point group is just O.
If n = 5, then the molecule has Icosahedral symmetry (I):
If there is a centre of symmetry then the point group is Ih
Otherwise, the point group is just I.
b) Is the molecule linear, i.e. can the molecule be rotated by any amount about one axis and
still look the same? If the molecule is linear…
If there is a mirror plane perpendicular to the rotation axis, the point group is D∞h
Otherwise the point group is C∞h.
c) Are there no rotation axes Cn? If this is true then…
If the molecule has a centre of symmetry (i), the point group is Ci
If the molecule has a plane of symmetry of symmetry (), then the point group is Cs
Otherwise, the point group is C1.
2) Identify the highest order rotation axis. This will now be denoted as the vertical (z axis).
NB from now on, horizontal and vertical are defined with respect to the vertical (z-axis)
specified in rule (2) – not necessarily the same as horizontal/vertical with respect to the way
the molecule has been drawn on a piece of paper!

3) Now look for C2 rotation axes perpendicular to the highest order axis. If these are present then
the molecule is dihedral (D). Note that there will either be no C2 axes perpendicular to the
highest order Cn axis or there will be n of them (e.g. if the major axis is C4 there will either be no
C2 axes or four of them). If you find one then you know that the others must also be present. If
the molecule is not dihedral, move on to rule (4). Otherwise…
If the molecule has a horizontal mirror plane, then it is Dnh
If the molecule has no horizontal mirror plane but does have vertical mirror planes, then the
point group is Dnd
Dnv might seem a more sensible name but Dnd is the way it is!
Vertical mirror planes are also present in Dnh but the horizontal mirror plane takes
precedence when defining the point group.
If vertical mirror planes are present, there will always be n of them (related to each other by
the Cn axis)
If there are no mirror planes then the point group is simply Dn.
4) Look for an S2n axis coincident with the Cn axis. If present then the point group is S2n.
5) Look for mirror planes…
If the molecule has a horizontal mirror plane, then it is Cnh

If the molecule has no horizontal mirror plane but does have vertical mirror planes, then the
point group is Cnv

If vertical mirror planes are present, there will always be n of them (related to each other by
the Cn axis)
If there are no mirror planes then the point group is simply Cn.

Flow Chart for Point Group Determination


Step 1: Special Cases
Steps 3-5: Other Cases

That all looks very complicated! Don’t panic though. With a bit of practice you will be able to
determine point groups quickly and reliably. Let’s look at the steps above in more detail using some
examples to illustrate the situations we may encounter.

Step 1: Special Cases


The special cases are usually quite obvious. They comprise:

a) Molecules with more than one high-order symmetry axis, i.e. the regular polyhedra or
anything based on them. For example, a tetrahedron (CH4) has four C3 axes, one along each
C–H bond; an octahedron (SF6) has three C4 axes; an icosahedron [B12H12]2– has six C5 axes.
In practice you are very unlikely to meet anything except the regular tetrahedron (point
group Td) and the regular octahedron (point group Oh). Only three molecules are known
with the Ih point group; see if you can find out what they are.
b) Linear molecules. Those that consist of two equivalent halves and therefore have a
horizontal mirror (N2, H2, F2, O=C=O, HC≡CH, HC≡C–C≡CH etc.) are D∞h. Others (HCl, NO,
HC≡N etc.) are C∞v.
c) Molecules with no axis of symmetry (i.e. no rotational symmetry operations except C1, a
360° rotation, which is of course just E and no rotation-reflection symmetry except possibly
S2, which is equivalent to inversion). Molecules that have point group Ci (containing only an
inversion centre) are very rare, though those of you undertaking the course in
crystallography should note that this symmetry is common for lattices and crystal structures.
The point group C1 is very common, comprising any molecule with no symmetry operations
other than E, such as a carbon atom with four different substitutents. Molecules containing
only mirror symmetry (e.g. some naphthalene derivatives) are also quite common.
A molecule with only a plane of A molecule with no symmetry elements
symmetry (point group Cs) (point group C1)

Step 2: Assign the Highest Order Axis


In many cases this will be the starting point of the search for the point group. The highest order axis
is usually quite obvious. Also known as the principal axis, this axis defines the vertical direction (i.e.
the z-axis). There is usually only one principal axis – if you find more than one you should normally
go back to Step 1. There are a couple of exceptions to this though: some molecules (e.g. ethane and
allene) have three C2 axes. Ethene has three C2 axes none of which is more important in symmetry
terms than any of the others. Thus you can choose any permutation of x, y and z for the three axes
but you must stick to your choice and not change the axis labels afterwards. For allene, one (and
only one) of the C2 axes is coincident with an S4 axis and this is thus chosen as the principal axis (see
example later in this handout).

Step 3: Check for Dihedral Molecules


If the molecule has n C2 axes all in the same plane (the horizontal plane) perpendicular to the
principal Cn axis, then it is dihedral and the point group symbol starts with a D. This condition is
fulfilled by any regular plane, such as a pentagon.
This has a C5 principal axis perpendicular to the
plane of the pentagon, and five C2 axes in the
plane, rotation about each of which would result in
flipping the pentagon over. Likewise, as you saw in
Lecture 1, BCl3 (a trigonal planar molecule) has
three C2 axes perpendicular to the principal C3 axis. One of the five C2
C5 axis
axes
If the plane has an axial substituent, the n perpendicular
C2 axes are no longer present. Although the symmetry of
the principal axis is maintained, a C2 rotation
perpendicular to this axis would flip the molecule upside-
down and place the substituent into an empty space,
leaving an empty space where the substituent was.

However, if there are two identical axial substituents (e.g. PF5 or trans-SF4Cl2) the dihedral condition
is maintained as two-fold rotations will swap the axial substituents with each other leaving the
molecule looking unchanged.
If the molecule is dihedral, it may be Dn, Dnd or Dnh depending on the presence and position of mirror
planes. The presence of a plane horizontal to the principal axis makes the molecule Dnh, which is by
far the most common type of dihedral point group encountered. All regular polygons fall into this
category; BCl3 is D3h, a square plane (such as XeF4) is D4h, and benzene is D6h.
A Dnh group also has to contain n vertical planes of symmetry (as
mentioned above), that include the n C2 axes, i.e. the C2 axes lie in these
planes. The four C2 axes for a D4h molecule are illustrated on the right and
the four vertical mirror planes coming out of the page will include these
four axes.
If there isn’t a horizontal mirror plane but instead there are n vertical
mirror planes passing between the C2 axes, then the group is Dnd. A good
example of this is staggered ethane. The three C2 axes are shown in the
end-on view (all in the plane of the paper, perpendicular to the principal C3 axis). Consider axis 2; a
C2 rotation will result in Ha and He trading
places, as will Hb/Hd and Hc/Hf. The three
vertical planes, each of which contain a set
of three bonds such as Ha–C–C–He, lie exactly
between these C2 axes; the axes are not in
the planes as they are for Dnh.

End-on view (looking If the molecule possesses no planes of


Staggered Ethane symmetry at all then the point group is Dn.
along z-axis)
These situations are rare. Note that molecules with Dn point groups are chiral as the groups lack any
mirror planes, inversion centres or rotation-reflection axes.

Step 4 Check for S2n Molecules


S2n point groups are very rare. A molecule belongs to an S2n point group if it has a rotation-reflection
axis S2n coincident with the highest order Cn axis without any (dihedral) C2 axes perpendicular to the
Cn axis. We have seen in the first lecture and workshop examples of molecules with rotation-
reflection axes: staggered ethane has an S6 axis coincident with the C3 (principal) axis and ferrocene
has an S10 axis coincident with the principal C5 axis. However, both of these molecules belong to
Dihedral point groups. It is very rare for a molecule to have a rotation-reflection axis without there
being dihedral axes. One example is B4N4Cl4Me4 which has the S4 point group; see if you can work
out its structure.

Step 5 Assign a Cnh, Cnv or Cn Point Group


Once you have got to this stage we know that the point group must begin with a C. Many molecules
fall into the remaining possible point groups. All we have to do now is look for mirror planes to
determine which point group is appropriate.
If there is a horizontal plane of symmetry, the point group is Cnh. An
example is trans-1,2-dichloroethane (with point group C2h). The C2h
point group must also possess inversion symmetry since C2.h = i.
Note also that unlike Dnh, no vertical mirror planes are present in Cnh
point groups. Cnh point groups other than C2h are very rare.
If the molecule has n vertical planes of symmetry, the point group is Cnv.
Water (C2v) is a good example (see first page of this handout). Ammonia
belongs to the C3v point group, since it has a C3 axis, is not dihedral and has
three vertical mirror planes. Each vertical mirror plane includes an N–H bond
and bisects the other two bonds in the molecule. The plane shown in the
diagram on the right contains the N–Ha bond and bisects the N–Hb and N–Hc
bonds.

If the molecule only has a Cn axis, with no planes of symmetry, then the point group is Cn. Cn
molecules are chiral, just as is the case for Dn.

Examples
Methyl Iodide, CH3I
1) Doesn’t belong to any special category
2) Highest order axis (in this case the only axis) is C3, along the C–I bond.
3) Not dihedral
4) Doesn’t have an S6 axis
5) No horizontal plane of symmetry but does have three vertical planes of
symmetry, each including the C–I bond and one of the C–H bonds.
Point Group = C3v

Allene, CH2=C=CH2
1) Doesn’t belong to any special category
2) There are three C2 axes. One is easy to see, along
the C=C=C bonds. This is denoted this as being the
z-axis. The other two are more difficult to visualise.
The diagram on the right with the hydrogen atoms
sitting at four of the corners of a box should help to
show you where they are.
3) The molecule is dihedral since it contains 2 axes
perpendicular the principal axis chosen in step 2.
There is not a horizontal mirror plane (Ha and Hb
would reflect into the empty spaces between Hc
and Hd leaving the molecule looking different).
However, it does have two vertical mirror planes,
one for each of the C=C=CH2 planes of atoms.
Point Group = D2d

Note that there is also an S4 axis in this molecule coincident with the principal C2 axis. The extra
symmetry associated with this axis is the reason for choosing this as the principal axis.

S41 and S43 are valid operations for this molecule. Why is S42 not a valid operation?

Think about the shape of a tennis ball including the joins. Does it also have a D2d point group?
Hydrogen Peroxide, H2O2
This can belong to one of three point groups depending upon its configuration.

Non-planar
One O-H bond is in front of the plane of the paper and the other O-H bond is
behind the plane of the paper. There are no other symmetry elements present
apart from C2.

Point Group = C2

Note that in this conformation the molecule is chiral.

cis-Planar
In this conformation, in addition to the C2 axis, the molecule now has vertical
planes of symmetry: one in the plane of the paper and the other bisecting
the molecule in half from left to right.

Point Group = C2v

Note that this molecule has the same point group as water – see page 1 of
this handout.

trans-Planar
The molecule still has a C2 axis but it now points perpendicular to the
plane of the molecule. Thus there is now a horizontal mirror plane.

Point Group = C2h

This molecule has the same shape as 1,2-trans-dichloroethene (see


above).

B6H10 (ignoring hydrogen atoms)


The boron atoms in this molecule have a C5 principal axis. The molecule is not
dihedral since two-fold rotation about an axis perpendicular to C5 would
result in Ba being swapped into the empty space at the bottom of the
molecule. There is no horizontal mirror plane but there are five vertical
mirror planes; each vertical plane contains the apical atom Ba and one of the
basal atoms Bb - Bf. The plane picked out in the diagram (the same plane as
that of the paper) contains Ba and Bb and interchanges Bc/Bf and Bd/Be.

Point Group = C5v


[B7H7]2– (a pentagonal bipyrimid)
Like B6H10 (the equivalent structure with one cap missing) the
principal axis is C5. However, this molecule is dihedral as the C2
axes in the pentagonal plane interconvert the equivalent boron
atoms at the top and bottom of the molecule leaving the
molecule looking unchanged. The additional capping boron
atom also results in the creation of a horizontal mirror plane.

Point Group = D5h